Cross-linked silanes



Patented Sept. 30, 1952 NIT -o;

CROSS-LINKED SILAN ES David B. Hatcher and Raymond H. Bunnell, To-

ledo, Ohio, assignors to Libbey-Owns-Ford Glass Company, Toledo,

bio

Ohio, a corporation. of

No Drawing. Application-January 6, 1950,

Serial No. 137,274

9 Claims;

The invention relates to novel hydrolyzable cross-linked silanes, whosemolecule contains at least two silicon atoms connected through carbonatoms.

The usual starting material for the production of organosiliconcompositions of the curable type is a mixture of silanes each of whosemolecules consists of a silicon atom to which are attached I fourmonovalent radicals, some of which are readily hydrolyzable and theothers of which are joined to the silicon atom through carbon atoms.Hydrolysis of such a mixture of silanes replaces each hydrolyzableradical with a hydroxy radical, and the hydrolysis ordinarily isaccompanied by condensation of part of thehydroxy radicals. H In suchcondensation, a hydroxy radical connected to one silicon atom condenseswith a hydroxy radical connected to another silicon atom to form anoxygen linkage between the two silicon atoms, with the production of onemolecule of water as a Icy-product.

Curable organosilicon compositions produced by the hydrolysis (withpartial condensation) of such a mixture of silanes can be used incoating, impregnating and laminating operations like mixture ofethylhalosilanes, of a substance whose molecule consists of two or moresilicon atoms which are connected throughcarbon atoms and to each ofwhich are attached hydrolyzable radicals produces an importantimprovement in the quality of the'silicone resin that is formed byhydrolysis of the mixture of ethylhalosilanes. The resulting modifiedethyl silicone resin produces clear, crack-free coatings which curefaster and are more flexible than coatings made from an unmodified ethylsilicone resin. I

The principal object of the invention is to provide novel hydrolyzablecross-linked silanes other curable condensation products, although Icurable organosilicon compositions are superior to other curablecondensation products in heat resistance and other properties.During'the curing of an organosilicon composition which is carried outto produce a finished coating, laminate or other product, thecondensation of the hydroxy radicals is substantially completed toproduce an infusib-le heat-resistant silicone resin.

The hydrolysis of pure diethyldichlorosilane (with condensation)produces a non-curable oil.

. United States Patent No. 2,258,220 discloses the production of curablecompositions by hydrolysis of a mixture of an ethyltrihalosilane with adiethyldihalosilane. However, it has been found that the curablecompositions whose production which are relatively inexpensive toproduce and which are highly advantageous for cohydrolysis with knownsilanes. More specific'objects and advantages are apparent from thedescription, which illustrates and discloses but is not intended tolimit the scopeof the invention.

An organosilicon compound embodying the invention has the generalformula n wherein R is an aromatic radical inwhich any atom other thancarbon and hydrogen consists of a, nuclear halogen having an atomicweight is disclosed in that patent have serious disadvantages. Coatingsmade of such compositions are subject to severe cracking and crazing.The cracking of such coatings may be due to excessive shrinkage uponcondensation or to the fact that the diethyldihalosilane upon hydrolysistends to form cyclic condensation products which are volatile andevaporate during the curing of the composition. The loss of. cycliccondensa tion products by evaporation tends .to cause shrinkage andcracking and leaves a resin which because of its low ethyl-to-siliconratio is excessively brittle.

It has been found that the addition, to such a less than 80, andin whichany exocyclic. carbon atom is contained in a methyl side chain; A is asaturated divalent aliphatic radical, having from one to three carbonatoms, in which the free valences are connected; through not more thantwo carbon atoms in series and in which any atom other than carbon andhydrogen consists of a halogen having an atomic weight between v 35 andX is a halogen having an atomic Weight less than 80; r is a saturatedprimary aliphatic hydrocarbon radical having fromone to three carbonatoms; m is an integer from 2 to 3; and n is an integer from Zto 3. s w

A halogen (X) attached to a silicon atom in a compound of the inventionmay be any halogen having anatomic weight less than 80 (i. e., chloro,

bromo, or fluoro).

A saturated primary aliphatic hydrocarbon radical having from one tothree carbon atoms (r) is a methyl, ethyl or 'n-propyl radical.

An aromatic radical (R) in which any atom other than carbon and hydrogenconsists of a nuclear halogen having an atomic weight less than 80, andin which any exocyclic carbon atom is contained'in a methyl side chain,maybe any radical having from'one to three benzene nuclei that containfromv 6 to 18 carbonatomsie. g.,

thracyl, 2,4-dimethyl anthracyl, bromophenyl,

o bromotolyl, o chlorotolyl,

bis (trichlorosilylethyl) benzenes, bis(trichlorosilylchloroethyDbenzenes, tris(trichlorosilylethyl) benzenes,bis trichlorosilylethyl) chlorobenzenes, tris(trich1orosily1 ethyl)chlorobenzenes, bis( trichlorosilylisopropyl) toluenes, tris(trichlorosilylisopropyl toluenes bis tricli-lcrosilylisopropylbenz'enes, tris,.( trichlorosilyllisQ ropyw benzenes,bis(ethyldichlorosilylethyl) toluenes, tris (ethyldichlorosilylethyl)toluenes, bis (trichlorosilylethyl) .0

toluenes, tris(trichlorosilylethyl) toluenes,bistri'chlorosilylisopropyl) dichlorobenzenes, tris(trichlorosilylisopropyll dichlorobenzenes, bis (trilchlo fOil lethyl)dichlorobenzenes, and tris (tri- 2-chloro-m-fiuorotolyl,2,6-dichlorotolyl, i-br'oj-s.

mo-o-xylyl, 4-bromo-m-xylyl, Z-bromo-p-xylyl, 3 bromo o xylyl,chlorophenyl, 1-.chloro-4 fluorophenyl, alpha-bromonaphthyl, beta-brombnaphthyl, 2-chloronaphthyl, l-bromo-3-chlo'ro naphthyl,2-chloro-1-methyl naphthyl, l-bromb- 8-methyl naphthyl,l-broiiio-l-methyl naphthyl, rh rQr .-metby1.@ anhthy l rqmo-Zmethvl r1,.:br m r -meth l enhth l, 8-brQmo-. 271119 .vl-nanhthvt-bromo-fi-znethvhn nhth l =br me fl einie h lr ph hyh evb omorlifie x.izl lcy'll,14 11mm;rzlli-din eth l. nhrv hyl. wmmszmeth l naphth li-brQmO: -1dimeth la1q h rhrqm -zm t yl1naphq 'bbmm .-methy.l,.n phth l;1 ,0- di b ITQmOI-l nthrec li l1 9.vdi hloroan hracyli henanthryll. rm tyl, h nenthltyt; nd ik-ldim thylphen ne thryl. 1 A a ur ted-idivalent-alhat dical; h vin mm, .oneto. th ee, carbon-atoms, -;-(Ai in which E heree, e nc s. are. cnn ct d throu h, not m r han We CBLIZDQII, tom ineries and; in With vM 111othe itm arbon anihy rw en. onsists i; a, a enhay n n t mic wei htibetween 1cm. 3911s, aidiralent aliphati hydrocarbonadiel -.which; ase aturat dw having from one' to' two carbon atoms orbyf the removal "of" two hydrogen atoms-from the same carbon atom. ortwo. adjacent carbon-atoms I in the molecule of .a -saturated aliphatichydrocarbon having three carbon atoms (i. e., the divalent hydrocarbonradical may be methylene, ethylene, -methy1 methylene, ethyl methylene,dimethyl methylene, or lor Z-methylethylne) or (2 by the removal of twohydrogen atoms from-a molecule as described in (1) inwhich a hydrogenatom has beenreplaced with-a chlorine .orbromine atom.

It is preferred that an organosiliconcompound embodying the invention.be-one having the general formula hereinbefore defined which" m is 3(for reasonshereinafter explained) It is preferred also that B have 'noside chains and that A have two carbon atoms, It is desirable that n be2 since a substance in which nis 2' is less expensive to produce'than asubstance in which'n is '3. It is desirable also that be chloro(for'reasons hereinafter-explained);

Substances embodying the invention-include? d bromo m-xylene 2 having-nosubstituent o radical. Such aromatic, comp,

'--chlorosilylethyl)dichlorobenzenes.

An organosiliconcompound embodying the invention can be. obtained byreacting in the presence-of an aluminum halide a composition comprisingtwo substances.

In such a reaction halogenatoms are split out of aliphatic radicals intwo or three molecules of one substance, and o: o three dr en toms-la elt: ut; of naromat niwl nsin l ne-m ecules he thcr ubs an e. 9 t t: he:eactms. mcleeules; re, linked into a single molecule by a ne o h e, Wesubst nc s, an, roma ic comp,o.und. Whose, ecu1e, c H tsof ,.-f19 one,o, three be zene, hat bn am; frame-1 Ti B rb iniiat ms. avma drosenatoms at: c eq i o l a tw ucl t T' etbmi t msavmsg qtmcrc an, L.- each;of, which lis a,

than Q .-an. .-hav-,-

three ,,nufc1 ear substitue halogen l tQ i W i ht ingf'n'of side chains,or' h a, three, side; chains, each er, which is,,a methyl benzene,toluene, xylenes, diphen naphthalene, ,l-methwl. naphthalen 2'emethylnaphthalene, at' tli'race'ne, 9 methy1.,anthraceh,. 2,3f-,dimethylanthracene 2,6ldini th'yl ,anthr'aev terph nyls;

'thaleh'e, 1 ronc '-i imet y naphthalene 1 -2e e.t 1

threne, 1,4 dimethylphenanthrene, ant i15 mand -pdichlorobenzenes v vThe other of thes'etwo substances is fahalo-- alk-ylsilane --whosemoleculeconsists of-'a silicon atom a to which care atta'che'dufourmonovalen t radicals one o f which is an alpha or beta-halosubstituted primary orsecondary aliphatic; hy-

drocarbori radical: having: frompgonee to: threes carbon atoms, .in'fwhichi the. halogen atomchas an atomic weight between 35 and.Iic./.(i.;e., a. chloro-Ior bromoesubstituted methylz radical; an

s: ncttmpr'e than. 5

.i ihlorce femeth ln phtha:

alph'a- 'or beta c'hloroor bromo-substituted ethyl radical; or'analphaor betachloro or bromo-substituted' propyl or isopropyl radical); fromtwo to three of which are halogens having an atomic weight less than 80;the remaining radical, if any, being asaturated primary aliphatichydrocarbon radical having from one to three carbon atoms (i.-e., amethyl radical, an ethyl radical .or an n-propyl radical). Suchhaloalkylsilanes include alpha chloroethyltrichlorosilane, betachloroethyltrichlorosilane, alpha chropropyltrichlorsilane,chloromethyltrichlorosilane, beta chloropropyltrichlorosibane, andalpha-chloroethyl-ethyldichlorosilane.

These haloalkylsilanes and others which may be1used to prepare compoundsof the invention are prepared by chlorinating or brominating suchsubstances as methyltrichlorosilane, ethyltrifiuorosilane,diethyldifluorosilane, isopropyltrifiuorosilane,ethyldifiuorochlorosilane, ethylfiuorodichlorosilane,-isopropyldifiuorochlorosilane, isopropylfiuorodichlorosilane,ethyltrichlorosilane, propyltrichlorosilana. propyltrifiuorosilane,diethyldichlorosilane, ethylpropyldichlorosilane,isopropyltrichlorosilane, ethylmethyldichlorosilane, andmethylpropyldichlorosilane. It is preferred that .the halogen atomintroduced into the aliphatic radical and the halogen atoms attachedtothe silicon atom be chlorine, since chlorine is a cheaper rawmaterial'than bromine. It is preferred that compounds embodying theinvention be formed from starting materials which arealkyltrihalosilanes. Better yields of the mono-chlorinated product canbe obtained by chlorination of a silane containing only one alkylradical. The chlorination of an alkyltrihalosilane, such asethyltrichlorosilane, is a clear cut reaction that proceeds smoothly andrapidly to give a mixture of unchlorinated ethyltrichloro silane,alpha-chloroethyltrichlorosilane, betachloroethyltrichlorosilane,alpha,beta-dichloroethyltrichlorosilane, and some polychlorinatedethyltrichlorosilanes. Beta-chloroethyltrichlorosilane is obtained inthe largest amount.

The method of chlorinating silanes to prepare haloalkylsilanes for useas starting materials for the preparation of compounds of the inventionmay comprise any desired procedure. For example, a chloro group may beintroduced bya liquid phase reaction in which molecular chlorine isbrought into contact with the liquid silane to be chlorinated.Ultraviolet light is required to conduct the reaction. The reaction isusually conducted at atmospheric, pressure and at a slightly elevatedtemperature, the maximum temperature at atmospheric pressure beinglimited by the boiling temperature of the silane to be chlorinated.Ibis-desirable that thechlorine be bubbled into the silane in order toavoid high local chlorine concentrations which are likely to result inburning of the silane and a corresponding darkening of the product. Thechlorination proceeds at such a rate in ordinary laboratory apparatusthat about one mol of a silane-can be chlorinated per hour when thechlorine is introduced through a singlejet. Ordinarily, about one mol ofchlorine is used per mol of silane to be mono-chlorinated but the amountthat is used can be regulated to control the extent of the chlorination.The silane is placed in a suitable reactor and chlorine is admitted (atthe bottom of the reactor.)- as comparatively small bubbles. Thechlorine can be dispersed by means of small glass Raschig rings placedat the bottom of the reactor. Ultraviolet light is used to catalyze thechlorination (e. g., from a high pressure mercuryvapor lamp equippedwith a filter which v absorbs all radiation havingv a wavelength shorterthan 2800 angstrom units, per cent of I the radiation having'a wavelength shorter than 34.00 angstromunits and 10 per cent of the radia-'0.. Chlorination of a silane can be conducted. The'chlorine is usuat arelatively rapid rate. ally introduced (as comparatively small bubbles)through a jet at a rate. not less than about 0.7 mol per hour (if it isdesired to chlorinate large quantities of a, silane, thechlorine can beintroduced simultaneously through each of two or more jets at thespecified rate) It is most desirable that the rate beat least about 0.9mol per hour, and not greater than about 1.1 moles per hour.

The reaction can be conducted continuously or as a batch process. Whenit is run continuously, theliquid silane is passed through a tube, andthe chlorine is admitted through jets along the length of the tube.The'amount of chlorine introduced per hour per jet is'such that-theratio of chlorine to silane does not give an explosive mixture at anypoint inthe reactor; the same considerations govern the amount ofchlorine when-the reaction isconducted continuously as when it isconducted batchwise. The jets should besofspaced that the temperature ofthe reaction mixture does not substantially increase or decreaseprogressively along the length of the reaction tube (i. e., the jetsshould be sufliciently far'apartso that the. temperature of the liquidinto which chlorine is introduced from any one jet is not substantiallyhigher than the temperature of the liquid into which chlorine isintroduced from any other jet).

The hydrogen chloride evolved during the chlorination is collected in awater scrubber. The amount of hydrogen chloride absorbed in thewaterpscrubber may be determined at intervals I by. titration withsodium hydroxide or potassium hydroxide, or the scrub water may bepassed into 'afiask containing the base and an indicator such as methylorange until the indicator shows the base to be neutralized.

The aluminum halide used in the preparation of compounds embodying theinvention is one in which each halogen atom has an atomic weight between35 and .806. e., aluminum chloride or aluminum bromide). Theterms"alu-minum chloride and aluminum bromide are used herein to meananhydrous aluminum chloride and anhydrous aluminum bromide The Ipreierr'ed aluminum halide is aluminum chloride.

, The procedure for contacting the aluminum halide with thehaloalkylsilane as hereinbefore defined) and the aromatic compound (asherein before defined) in order to prepare compounds of, t he. inventioncomprises adding the aluminum halide in small portions to a mixture ofthe halo-v alkylsilane and; the aromatic compound. Usuy; the -firstportion of the; aluminum halide 2&1 2321 7 (2% .to. %'0f';t0ta1 amountto be added)v :issadtde very carefully at .room temperature to the re.-action mixture, whi'chis then heated for about 2.0 -.minute s. Theremainder of the aluminum .halide is :then added :in portions. large.enough aluminum halide'is-maintained; att themimmum V necessary forreaction, fit. .is. lzpossible: -;to. .isolate the pure product; .byTdOUblB distillation. It is usually desirable, :however, to. remove "the:cat-

alyst before distillation; for :examplegby adding to the: reactionmixture .phosphorus :mcychlor-ide, which 'binds'. aluminumzchlonde.byreacting: with it to form'a stable :complexpAnamount of phosphorus'oxychlori-dezequiva'lent to the amount of aluminum chloride-presentinthereaction mixture (or: in slight;;excess:. over-the: amount 30faluminum chloride) :is added 1 to. the a reaction mixture when themixture "hastcooled' to .-a' temperature slightly below. thethoilingpoint of phos-. phorus oxychloride (107 0.). After further cooling an.amount :of a hydrocarbon solvent equal to the volumenfthe: reaction;mixture .is added to precipitate the A'lClaPOCla complex. Suchhydrocarbon. -:.solvents finclude' pentane, :ligroineand. petroleumethers. ..'The mixture is allowed to stand overnight, and? the solidcom- .plex- .ist .filteredi from thezsolution: or the liquid to *bedistilled 'zis'. decanted 1; from "the mixture, leaving. a :residue"containing the "A'lClazPOCla complex: An absorbing. :agent': such: as.kieselguhr may be. vaddedrrin place ofor infladdition to' 1 the3'hydrocarbonicsolvent to absorb .the AlC'lazBOClz complex,:and after.the reaction mixture cools to room temperature: thefiliquidrtonbedistilled may be. filtered "from. the absorbed complex; ThereisLlessrchance:thatialuminum;.chlo ridewill distill'withithe.productawhenz-it is in the .formsof: a complxxthanwhenit is-in thefree-"state, andwhen this complex is relatively non-volatile as compared:to. the worganosi-l'ane productzthe product may-:be -disti1lcd underreduced pressure in the: presence .of: theAlClsiPOCla complex.

.The aluminum halide should not. bezaddedin excess .of about 5 molepercent. base'd upon the amountof haloalkylsilane present inthe reactionmixture). It is most desirable that the amount of the aluminum halideused. -benot more than about 2 mole per cent-and not :less than about.75 mole percent.

It is desirable to 'use anexcess'of haloalkyle silane over aromaticcompound in order-to obtain a highyield of the compounds'embodying theinvention. The amount of haloalkyls'ilane should be not-less than-aboutl mole' -perpmole of aromatic compound, and it is preferredthat it benot less than" about 1;.5*moles;per--mole of aromatic compound. -Itispreferred that, the molar ratio of haloalkyl-silane to-aromatic compoundbe not more than about 2.5 to l; and most desirable that it be notmorethan about-21:01, although .ny-larger ratio that'givesa-substa ntialyield of-the desired product may be-used. On the other hand; ifan-excessofaromatic compound over haloalkylsilane is reacted accordingto the procedure hereinbefore-described;' 1or examplefismolesiofaromaticIcompQu-nd per-mole of: haloalkylsilane, a large yield of: amono(silyalalkyll aromatic compound isobtained. ,Compounds embodying theinventioncan be obtained byzreacting in :thepresence .ofxan aluminumhalide. .(zas lhereinbef-ore: described): sucha mono- (si1yla1kyl)aromaticicompound with an. additional amount. of :the .haloalkylsilaneused .inthe prep: aration. -.ofthe. mono( silylalkyllaromatic com-.pound .j}. v

Substances; embodying the invention, having the .generalformulahereinbefore defined,i i-n which. gis .:a. halo-. substituted divalentaliphatic radical '(as ih'ereinbefore described) are prepared by:chlorinating or brominating .an- -organosilicon compound .of; theinvention produced by the. reactionofa:haloalkylsilaneand an aromaticcompound inthe presence of analuminum halide(as-xhereinbeforedescribed). .Itis preferred that thejhal'ogen. atomintroduced. into. the. divalent aliphaticgjradical be chlorine, sincechlorine is a :cheapen raw material than bromine. The method. of ch-lQinating may be the one using illtrayiolet -light, ashereinbei'ore.described orrany other-:miethod. When thearyl groupiin anor-.. eanosilicon compoundof the invention contains methyhradicals;halogenationmay take placeon the methyl: -ra,dicals= Thusthecompoundto'be halogenated.preferably: is one having. the generalformula: hereinbeforez. defined in which 'R' con-.. tains noisidechains. Compounds, embodying the. invention may be repared by one of;the proceduresv described in theziollowing .-:examp18.s.:,

Exa le, 1.

A =haloalkylsila'ne' (2 2? mols of. beta-chloroeth-yltr-ichlorosil ane);is :mixed with an aromatic compound (1.36 mols of benzene) in-a 1 liter3-necked flask equipped Witha mercury sealed stirrer-and a refluxcondenser-fittedwith a calcium-chloride tube. The mixture is stirred.and gently heated while-an aluminum halide .(2 mol per cent of aluminumchloride based on the amount of haloallgylsilane) isadded in smallportions over-a period of'one hour. After the additionof aluminumchloride is completed, the mixture isrefluxed} for one hour. Themixtureis then cooled-toabout 95-degrees C. and'phosphorusoxychloride ('5-cc.-) is added to complex the-aluminum chloride. After further cooling,

' a hydrocarbon solvent (500cc. of Sohio' S. R.

fiol-venti a petroleum fraction composed mainly of aliphatic hydrocarbon=mater-ial, boiling withinthe-r-ange to. 286- degrees 'F.) is added toprecipitatethe Alls-.POl3-complex. The mixture i s allowedtostandovernight and is then filtered. The filtrate ispla-ce'in a 1 literClaisen flask andthe excess hydrocarbon solvent-is distilled-atatmospheric pressure. The residue is then distilled at reduced pressureto recover all the material boiling-at temperatures up to 220 degrees C.at 1 mm. Hg (absolute pressure). Thismaterial is distilled to yield afraction (134 grams), B. P. 154-174 degrees C. at l-mm. Hg.This-fraction is redistilled to yield a-bis(2-trichlorosilylethyl)benzene, B. P; l55-l65-degrees C. at I-"mnIHg.

Ewample 2 nhaloalkylsilane ('1- molof-beta-chloroethyltr-ichlorosilane)- and an aromatic hydrocarbon (1-6mol o'f -chlorobenzene)' are placed in a 1 liter three-necked flashequipped with a -mercury sealed sti-rrer-and-a reflux condenser fittedwith 9-- a calcium chloride tube. The mixture 'isgently heated andstirred While an aluminum halide (2 mol per cent of aluminum chloridebased on the amount of haloalkylsilane) is added in small portions'overa period of forty minutes. The mixture is then refluxed for about threemore hours. The mixture is cooled to a temperatureof about 95 degrees C.and phosphorusoxychloride (3.2 cc.) is added to complex the aluminumchloride. After further cooling, a hydrocarbon solvent (275 cc. of SohioS. R. Solvent) is added to precipitate the AlCkPOCh complex; The mixtureis allowed to stand overnight and is then filtered. "The filtrate isplaced in a 1 liter Claisen flask and the excess hydrocarbon "solvent isdistilled at atmospheric pressure. The residue is then distilled underreduced pressure to yield a bis(2-- trichlorosilylethyl)chlorobenzene(49 grams), B. P.-192'-195 degrees C. at l'mm. Hg.

Example 3 n (a) By a procedure similar to that described in thepreceding examples beta-chloropropyltrichlorosilane is reacted withtoluene toiobtain a mixture comprising a bis(Z-trichlorosilylisopropy1toluene and fa tris(2-trichlorosilylisoproyl)toluene. I r

(b) By a procedure similartothat described in the preceding "examples'b'eta chloropropyltrichlorosilane is reacted with'benzene to obtain amixturecomprising a bis( 2-'trichlorosilylisopropyDben'zene and a tris(ztrichlorosilylisopropyl) benzene.

(o) By a procedure similar to that described inthe preceding examplesalphaor beta-chloroethylethyldichlorosilane is reacted with toluene toobtain a mixture comprising a bis(ethyldichlorosilylethyl)toluene and atris(ethyldichlorosilylethyl)toluene.

(11) By a procedure similar to that described in the preceding examplesalpha-chloroethyltrichlorosilane is reacted with toluene to obtain amixture comprising a bis(l-trichlorosilylethyl)- toluene and atris(l-trichlorosilylethyl) toluene.

(a) By a procedure similar to that described in the preceding examplesalpha-chloroethyltrichlorosilane is reacted with chlorobenzene to obtaina mixture comprising a bis(l-trichlorosilylethyDchlorobenzene and atris(l-trichloros1lylethyl) chlorobenzene.

(1) By a procedure similar to that described in the preceding examplesbeta-chloropropyltrichlorosilane.ando-dichlorobenzene are reacted toobtain a mixture comprising abis(beta-trichlorosilylisopropyl)dichlorobenzene and a tris(beta'trichlorosilylisopropyl) dichlorobenzene.

(g) By a procedure similar to that described in the preceding examplesbeta-chloroethyltrichlorosilane is reacted with o-dichlorobenzene toobtain a mixture comprising a bis(2-trichlorosilylethyl) dichlorobenzeneand a tris(2-tricholorsilylethyl) dichlorobenzene.

Example 4 sealed stirrer and a reflux condenser fitted with a calciumchloride tube. Aluminum chloride (0.55 gram) is added to the stirredmixture in small portions. The mixture is heated gently for about twentyminutes. The heating is then discontinued for twenty minutes duringwhich time HCl is evolved vigorously. The mixture is again 10 heated for35 minutes before distilling under reduced pressure to yield crudebeta-phenylethyltrichlorosi'lane (52 grams) B. P. 164-174 degrees C. atmm. Hg. This product is redistilled under "reduced pressure to yieldcolorless betaphenylethyltrichloro'silane, B. P. 107-108 a grees C. at 2mm. Hg. 'Anaralykylsilane (397 grams of beta-phenylethyltrichlorosilaneprepared by severalruns according 'to the procedure described in thepreceding'paragraph) is mixed with a haloalykyl silane (109 grams ofbeta-chloroethyltrichloro silane), and an aluminum halide (1.47 ramsoraluminum chloride) is added, using the apparatus and procedure describedin Example 1 f After the addition of aluminum chloride is completed, themixture is refluxed for five hours? The mixture is then cooled to aboutdegrees-"C. and phosphorus oxychloride (1.4. cc.) is" added to complexthe aluminum chloride. After further cooling, a hydrocarbon solvent (500cc. of Sohio S. R. Solvent) is added to precipitate the AlCl3.POCl3complex." The mixture is allowed to stand overnight and is thenfiltered. 'Ihe-fll-v trate' is placed in a l liter Clais'en flask andthe excess hydrocarbon solvent is distilled-at atmospheric pressurebefore distilling at reduced pressure to obtain a fraction (57 grams) B.P. 65 degrees C; at 20 mm. Hg to 117 degrees C. at l l mm. Hg and another fraction (274 'grams'),B'-. P. 117 degrees C. at 14 mmQI-Ig toliifl'degre's C; at 1 mm. Hg; This latterfract'ion' is 'redistilled torecover unreacted beta-phenylethyltrichlorosilane (124 grams). Theresidue from this redistillation is combined with 138 grams of residuefrom the first fractionation, and the mixture is distilled t yield abis(2-trichlorosilylethyl)benzene (134 grams), B. P. 155-159 degrees C.at 1 mm. Hg.

Example 5 at the bottom with Raschig rings (to a height of about 5 cm.)and fitted with a gas inlet tube (having an internal diameter of about 6mm.) which is sealed through the bottom of the chlo. rination (reactor)tube so that the chlorine is discharged vertically (near the bottom ofthe reactor) into the organosilicon compound. The top of the reactortube is fitted with a Dry-Ice condenser and a glass tube which conductsany gases not condensed in the Dry-Ice condenser to a water scrubberwhere the HCl formed by the chlorination is removed. The chlorinationtube is illuminated with ultra-violet light from a Mazda CPI-4; wattultraviolet lamp. As chlorine gas is introduced into the chlorinationtube, the evolved HCl is passed from the top of the Dry-Ice condenser tothe scrubben The scrub water is passed into a flask containing anequivaethylphenyl) beta chloroethyltrichlorosilane,

with-small uantities-erabis-(beta-trichlorosilylalpha-.chlomethyl)henzene; .2. bisCbeta-trichlorosillyl-beta-chloroethyl) benzene; :a :beta -.(,2: --trichlorosilylethylphenyh alpha chloroethyltrichlorosi-lane andabeta-(-2atrichlorosilyl-sbetachloroethylphenyl) beta ---ch1oroetlry-1trichlorosilane. v Y

.Other. vorganosil-ieon compounds of. the invention may be producedby.ch-lorinating the procedure describedv in. the preceding paragraph the,iollowing compounds (prepared as herein- .heioredescribed): his and-tris(\trich1orosi1 y1- ethylJ-chlorobenzenes, his and:tristtrichloresilylisopropyllbenzenes, his and tris(-trich1orosily1-ethyl) dichlorobenzenes, and his and tris(trich-1oros-ilyl-isopropyl)d-ic-h-lorobenzenes.

Wit-claim:

v1. An-organosi-liconcompoundhavingthe general .formula wherein R is anaromatic radical in which any atom other than oarbontand hydrogenconsists of a nuclear halogen having anatomic weight less than 80, and.inwhicnany exocycliccarbon atom isv contained ina methyl side chain;.A-is'a saturated divalent aliphatic radical, having from one to threecarbon atoms, in which the .free valences are connected through not mor:v than twowoarbon atoms in series and in which any 12 atom other thancarbon and hydrogen consists of aha-logenhaving anatomic weight betweenand-18.0; X is-sa; halogen having an atomic weight-less- .tha-ni; ,risasaturated primary aliphatichydroc'arbon radical having from one to thneecarboneatoms; mis an integer from 2 to 3; .andin'isanfin-teger from 2 to3. v I

22. :An -orga nosi1icon compound as claimed in claim :1 .in whichcm 153.

An :erganos-ilicon compound as claimed in claim 2 in whicnR :has sixcarbon atoms.

An organosi-licon compound as claimed in claim- 3 in which. .A- :has"two carbon atoms.

.5; An organosilicon compound as claimed in claim 4' in' w-hich-11,-.-is2-.

6.1m organosil-icon compound as claimed in claim 5- in which X-ischloro.

7. YA. 'bis(2 trichlorosilylethyl benzene.

:8. .A bis(2-trich1onosilylethyl)chlorobenzene.

9. A 2-(2-trichlorosilylethylphenyl) -2-ch1oroethyltrichlorosilane'.

DAVID .B'. 'HATCHER. RAYMOND H. BUNNELL.

:REEERENCES- CITED The foilowi-ng references are of record in the fileof this patent:

UNITED SZIATESIPA'I'ENTS Number Name Date 23785493 Levine ..s :Aug. 9,1949 2;.486',1-.6.2- Hyde Got. 25, .1949

1. AN ORGANOSILICON COMPOUND HAVING THE GENERAL FORMUAL